The Toxicity of Graphene Oxides: Dependence on the Oxidative Methods Used

Graphene, a class of two‐dimensional carbon nanomaterial, has attracted extensive interest in recent years, with a significant amount of research focusing on graphene oxides (GOs). They have been primed as potential candidates for biomedical applications such as cell labeling and drug delivery, thus the toxicity and behavior of graphene oxides in biological systems are fundamental issues that need urgent attention. The production of GO is generally achieved through a top‐down route, which includes the usage of concentrated H₂SO₄ along with: 1) concentrated nitric acid and KClO₃ oxidant (Hoffmann); 2) fuming nitric acid and KClO₃ oxidant (Staudenmaier); 3) concentrated phosphoric acid with KMnO₄ (Tour); or 4) sodium nitrate for in‐situ production of nitric acid in the presence of KMnO₄ (Hummers). It has been widely assumed that the properties of these four GOs produced by using the above different methods are roughly similar, so the methods have been used interchangeably. However, several studies have reported that the toxicity of graphene‐related nanomaterials in biological systems may be influenced by their physiochemical properties, such as surface functional groups and structural defects. In addition, considering how GOs are increasingly used in the field of biomedicine, we are interested to see how the oxygen content/functional groups of GOs can impact their toxicological profiles. Since in‐vitro testing is a common first step in assessing the health risks related with engineered nanomaterials, the cytotoxicity of the GOs prepared by the four different oxidative treatments was investigated by measuring the mitochondrial activity in adherent lung epithelial cells (A549) by using commercially available viability assays. The dose–response data was generated by using two assays, the methylthiazolyldiphenyl‐tetrazolium bromide (MTT) assay and the water‐soluble tetrazolium salt (WST‐8). From the viability data, it is evident that there is a strong dose‐dependent cytotoxic response resulting from the four GO nanomaterials tested after a 24 h exposure, and it is suggested that there is a correlation between the amounts of oxygen content/functional groups of GOs with their toxicological behavior towards the A549 cells.     

Highly Hydrogenated Graphene through Microwave Exfoliation of Graphite Oxide in Hydrogen Plasma: Towards Electrochemical Applications

Hydrogenated graphenes exhibit a variety of properties with potential applications in devices, ranging from a tunable band gap to fluorescence, ferromagnetism, and the storage of hydrogen. We utilize a one‐step microwave‐irradiation process in hydrogen plasma to create highly hydrogenated graphene from graphite oxides. The procedure serves the dual purposes of deoxygenation and concurrent hydrogenation of the carbon backbone. The effectiveness of the hydrogenation process is investigated on three different graphite oxides (GOs), which are synthesized by using the Staudenmaier, Hofmann, and Hummers methods. A systematic characterization of our hydrogenated graphenes is performed using UV/Vis spectroscopy, SEM, AFM, Raman spectroscopy, FTIR spectroscopy, X‐ray photoelectron spectroscopy (XPS), combustible elemental analysis, and electrical conductivity measurements. The highest hydrogenation extent is observed in hydrogenated graphene produced from the Hummers‐method GO, with a hydrogen content of 19 atomic % in the final product. In terms of the removal of oxygen groups, microwave exfoliation yields graphenes with very similar oxygen contents despite differences in their parent GOs. In addition, we examine the prospective application of hydrogenated graphenes as electrochemical transducers through a cyclic voltammetry (CV) study. The highly hydrogenated graphenes exhibit fast heterogeneous electron‐transfer rates, suggestive of their suitability for electrochemical applications in electrodes, supercapacitors, batteries, and sensors.     

Unusual Inherent Electrochemistry of Graphene Oxides Prepared Using Permanganate Oxidants

Graphene and graphene oxides are materials of significant interest in electrochemical devices such as supercapacitors, batteries, fuel cells, and sensors. Graphene oxides and reduced graphenes are typically prepared by oxidizing graphite in strong mineral acid mixtures with chlorate (Staudenmaier, Hofmann) or permanganate (Hummers, Tour) oxidants. Herein, we reveal that graphene oxides pose inherent electrochemistry, that is, they can be oxidized or reduced at relatively mild potentials (within the range ±1 V) that are lower than typical battery potentials. This inherent electrochemistry of graphene differs dramatically from that of the used oxidants. Graphene oxides prepared using chlorate exhibit chemically irreversible reductions, whereas graphene oxides prepared through permanganate‐based methods exhibit very unusual inherent chemically reversible electrochemistry of oxygen‐containing groups. Insight into the electrochemical behaviour was obtained through cyclic voltammetry, chronoamperometry, and X‐ray photoelectron spectroscopy experiments. Our findings are of extreme importance for the electrochemistry community as they reveal that electrode materials undergo cyclic changes in charge/discharge cycles, which has strong implications for energy‐storage and sensing devices.     

Graphenes Prepared by Hummers,Staudenmaier and Hofmann Methods for Analysis of TNT‐Based Nitroaromatic Explosives in Seawater

The detection of TNT and related nitroaromatic compounds in seawater is of great interest. Electrochemical techniques can be applied for detection purposes since nitroaromatic compounds contain easily reducible nitro groups. In this study, we investigate the performance of thermally reduced graphenes prepared by three different oxidative methods: Hummers, Staudenmaier and Hofmann methods with consequent thermal exfoliation. The Hofmann method‐based graphene was found to exhibit the highest sensitivity in detecting TNT electrochemically. Extended study on the detection of TNT in seawater using the graphene material provided significant improvements in the detection sensitivity. These findings will have profound impacts on the detection of nitroaromatic explosives in seawater.     

Graphene Oxides Prepared by Hummers’, Hofmann’s,and Staudenmaier’s Methods: Dramatic Influences on Heavy‐Metal‐Ion Adsorption

Graphene oxide (GO), an up‐and‐coming material rich in oxygenated groups, shows much promise in pollution management. GO is synthesised using several synthetic routes, and the adsorption behaviour of GO is investigated to establish its ability to remove the heavy‐metal pollutants of lead and cadmium ions. The GO is synthesised by Hummers’ (HU), Hofmann’s (HO) and Staudenmaier’s (ST) methodologies. Characterisation of GO is performed before and after adsorption experiments to investigate the structure–function relationship by using Fourier‐transform infrared spectroscopy and X‐ray photoelectron spectroscopy. Scanning electron microscopy coupled with elemental detection spectroscopy is used to investigate morphological changes and heavy‐metal content in the adsorbed GO. The filtrate, collected after adsorption, is analysed by inductively coupled plasma mass spectrometry, through which the efficiency and adsorption capacity of each GO for heavy‐metal‐ion removal is obtained. Spectroscopic analysis and characterisation reveal that the three types of GO have different compositions of oxygenated carbon functionalities. The trend in the affinity towards both Pb^II and Cd^II is HU GO>HO GO>ST GO. A direct correlation between the number of carboxyl groups present and the amount of heavy‐metal ions adsorbed is established. The highest efficiency and highest adsorption capacity of heavy‐metal ions is achieved with HU, in which the relative abundance of carboxyl groups is highest. The embedded systematic study reveals that carboxyl groups are the principal functionality responsible for heavy‐metal‐ion removal in GO. The choice of synthesis methodology for GO has a profound influence on heavy‐metal‐ion adsorption. A further enrichment of the carboxyl groups in GO will serve to enhance the role of GO as an adsorbent for environmental clean‐up.     

Enhanced adsorption performance of the graphene oxide with metallic ion impurities by elution

The graphene oxides (GOs) with various content of metallic ions impurities were prepared, and the adsorption performance of the GO before and after elution was evaluated. The prepared GOs were characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, inductively coupled plasma and atomic force microscopy. The results indicated that the metallic ion impurities hardly affected the interlayer distance, microstructure and thickness of the prepared GOs. The adsorption isotherm and adsorption kinetic results showed that the metallic ions adsorbed on the GO surface had a negative influence on both the adsorption capacity and rate. After eluted by HNO₃ or HCl, most of the metallic ions adsorbed on the GO‐91 surface were ion‐exchanged by the protons of the acid eluents, and the purified GO showed enhanced equilibrium capacities and improved adsorption rate. The elution efficiency of HCl was better than that of HNO₃, and the adsorption capacity and rate of the GO eluted by HCl approximately reached to those of the GO prepared from the graphite with high purity. It indicated that HCl could efficiently remove the metallic ions adsorbed on the GO surface. Copyright © 2017 John Wiley & Sons, Ltd.     

Preparation of graphene oxide-coated silk fibers through HBPAA [a molecular glue]-induced layer-by-layer self-assembly

Carbon nanomaterials recently gained extensive interests for their good application potential in composite nanomaterials because of their unique physicochemical properties. In this study, graphene oxide (GO)-coated silk fibers were fabricated through HBPAA-induced layer-by-layer (LbL) self-assembly technology. The closely adhered GOs coatings were achieved by circular incubation with solutions of hyperbranched poly (amidoamine) (HBPAA) and GOs, with HBPAA serving as the “molecular glue” that could bind single or mutilayered GOs to the surface of silk fibers. In the experiments, GOs nanosheets were synthesized by a modified Hummers method and were characterized by atomic force microscopy, transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Our developed technology was able to tightly bind GOs to the silk surface and control their loading capacity. Owing to the positive charges and abundant amino end groups of HBPAA, GOs were found to be completely adsorbed onto silk surface. Therefore, their assembly would be green and controllable. The Fourier transform infrared (FTIR) spectroscopy, XPS, XRD, Thermogravimetric analyses (TGA) confirmed the attachment of HBPAA and GOs. Field mission scanning electron microscopy (FESEM) indicated that GOs closely spread on the surface of silk fibers without any self-folding though excessive stacking were observed in a small part of a silk surface with the increased density of GOs coatings. The developed LbL self-assembly technology may provide a controllable approach to coat GOs on the surface of biological fibers and graphene-based functional materials.     

Building up polymer architectures on graphene oxide sheet surfaces through sequential atom transfer radical polymerization

The reactivity between the active species of atom transfer radical addition and the unsaturated groups of graphene oxides (GOs) has been demonstrated in this work. The reaction and the sequential surface‐initiated atom transfer radical polymerization provide a convenient approach to anchor various polymer chains and to buildup various polymer architectures, such as linear polymer, V‐shape block polymer, multibonded polymer layer, and hierarchical brush‐on‐layer polymer, on GO sheet surfaces. The chemical structures and morphology of the polymer‐modified GOs have been characterized with Fourier transform infrared spectroscopy, Raman spectroscopy, X‐ray photoelectron spectroscopy, and atomic force microscopy. After organomodification, the GOs exhibit a good dispersion ability in organic solvent over 80 days, amphiphilic characteristics, and temperature‐responsive properties. Reduction of the GOs has been performed to result in graphene‐like materials showing certain extent of electron conductivities. An effective approach to synthesize GO/polymer hybrid materials possessing various polymer architectures and attractive properties has been developed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1588–1596     

Investigation of the Thermal Stability of the Carbon Framework of Graphene Oxide

In this study, we use our recently prepared graphene oxide (GO) with an almost intact σ‐framework of carbon atoms (ai‐GO) to probe the thermal stability of the carbon framework for the first time. Ai‐GO exhibits few defects because CO₂ formation is prevented during synthesis. Ai‐GO was thermally treated before chemical reduction and the resulting defect density in graphene was subsequently determined by statistical Raman microscopy. Surprisingly, the carbon framework of ai‐GO is stable in thin films up to 100 °C. Furthermore, we find evidence for an increase in the quality of ai‐GO upon annealing at 50 °C before reduction. The carbon framework of GO prepared according to the popular Hummers’ method (GO‐c) appears to be less stable and decomposition starts at 50 °C, which is qualitatively indicated by CO₂‐trapping experiments in μm‐thin films. Information about the stability of GO is important for storing, processing, and using GO in many applications.     

氧化环境和比例对改性Hummers法制备GO的影响

以鳞片石墨(GR)为原料,采用改性Hummers法液相氧化方法制备氧化石墨,通过超声剥离的方法剥离出片状的氧化石墨烯(GO),探讨了H₂SO₄环境与H₂SO₄+H₃PO₄混酸环境和KMnO₄与GR的比例对GO制备的影响。采用FTIR、UV、TG、XRD、SEM和XPS等分析手段对制备的GO进行分析。结果表明：GO外貌是呈褶皱片状,在片层上主要有C=O、C-OH、-COOH和C-O-C等官能团,以共价键形式存在石墨层间;通过TG与XPS数据分析表明在H₂SO₄ H₃PO₄混酸环境下制备的GO含氧官能团较多,并且(KMnO₄)与鳞片石墨的最佳比例是1:4。     

Effect of potassium permanganate on morphological,structural and electro-optical properties of graphene oxide thin films

This work investigated the effect of Potassium Permanganate (KMnO₄) on graphene oxide (GO) properties, especially on electrical properties. The GO thin films were deposited on a glass substrate using drop casting technique and were analysed by using various type of spectroscopy (e.g. Scanning Electron Microscopy (SEM), Ultra- Violet Visible (UV–VIS), Fourier Transform Infrared (FTIR), X-Ray Diffraction (XRD), optical band gap, Raman Spectroscopy). Furthermore, the electrical experiments were carried out by using current–voltage (I-V) characteristic. The GO thin film with 4.5 g of KMnO₄ resulted in higher conductivity which is 3.11 × 10^?4 S/cm while GO with 2.5 g and 3.5 g of KMnO₄ achieve 2.47 × 10^?9 S/cm and 1.07 × 10^?7 S/cm, respectively. This further affects the morphological (SEM), optical (band gap, UV–Vis, FTIR, and Raman), and crystalline structural (XRD) properties of the GO thin films. The morphological, elemental, optical, and structural data confirmed that the properties of GO is affected by different amount of KMnO₄ oxidizing agent, which revealed that GO can potentially be implemented for electrical and electronic devices.     

Surface Modification of Graphene Oxides by Plasma Techniques and Their Application for Environmental Pollution Cleanup

Graphene oxides (GOs) have come under intense multidisciplinary study because of their unique physicochemical properties and possible applications. The large amount of oxygen‐containing functional groups on GOs leads to a high sorption capacity for the removal of various kinds of organic and inorganic pollutants from aqueous solutions in environmental pollution cleanup. However, the lack of selectivity results in difficulty in the selective removal of target pollutants from aqueous solutions in the presence of other coexisting pollutants. Herein, the surface grafting of GOs with special oxygen‐containing functional groups using low‐temperature plasma techniques and the application of the surface‐modified GOs for the efficient removal of organic and inorganic pollutants in environmental pollution are reviewed. This paper gives an account of our research on the application of GO‐based nanomaterials in environmental pollution cleanup, including: (1) the synthesis and surface grafting of functional groups on GOs, summarizing various types of low‐temperature plasma techniques for the synthesis of graphene/GOs; and (2) the application of graphene/GOs and their composites for the efficient removal of organic and inorganic pollutants from aqueous solutions, including the interaction mechanism according to recently published results.     

Effect of preparation methods of graphene oxide on permeability of free-standing membranes against polar and nonpolar species

ABSTRACT

In this study, graphene oxide (GO) was synthesized using Hummers, modified Hummers and improved Hummers methods, and then freestanding membranes were prepared based on these materials. Effects of different GO preparation methods on C/O ratio and interlayer spacing of freestanding membranes were studied. Structure of these membranes was studied by X-ray diffraction, contact angle, XRF, FT-IR, and FESEM methods. Also, permeability of ammonia, dichloromethane, and water vapor was investigated through these membranes. Results showed that, the sample prepared by the Hummers method had lower C/O ratio, smoother surface and lower permeability for polar species, such as water and ammonia vapors, than nonpolar materials. Membranes prepared using Improved Hummers method showed the least permeability against nonpolar vapors such as dichloromethane.     

Nickel‐substituted cobalt ferrite nanoparticles supported on arginine‐modified graphene oxide nanosheets: Synthesis and catalytic activity

The amino acid arginine was used to modify the surface of graphene oxide nanosheets and then nickel‐substituted cobalt ferrite nanoparticles were supported on those arginine‐grafted graphene oxide nanosheets (Ni_0.5Co_0.5Fe₂O₄@Arg–GO). The prepared Ni_0.5Co_0.5Fe₂O₄@Arg–GO was characterized using flame atomic absorption spectroscopy, inductively coupled plasma optical emission spectrometry, energy‐dispersive spectroscopy, Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, Raman spectroscopy, X‐ray diffraction, thermogravimetric analysis, scanning electron microscopy and transmission electron microscopy. The application of Ni_0.5Co_0.5Fe₂O₄@Arg–GO as a catalyst was examined in a one‐pot tandem oxidative cyclization of primary alcohols with o ‐phenylenediamine to benzimidazoles under aerobic oxidation conditions. The results showed that 2‐phenylbenzimidazole derivatives were successfully achieved using Ni_0.5Co_0.5Fe₂O₄@Arg–GO nanocomposite catalyst via the one‐pot tandem oxidative cyclization strategy.     

Endoperoxides Revealed as Origin of the Toxicity of Graphene Oxide

Potential biomedicinal applications of graphene oxide (GO), for example, as a carrier of biomolecules or a reagent for photothermal therapy and biosensing, are limited by its cytotoxicity and mutagenicity. It is believed that these properties are at least partially caused by GO‐induced oxidative stress in cells. However, it is not known which chemical fragments of GO are responsible for this unfavorable effect. We generated four GOs containing variable redox‐active groups on the surface, including Mn²⁺, C‐centered radicals, and endoperoxides (EPs). A comparison of the abilities of these materials to generate reactive oxygen species in human cervical cancer cells revealed that EPs play a crucial role in GO‐induced oxidative stress. These data could be applied to the rational design of biocompatible nontoxic GOs for biomedical applications.     

改进液相氧化还原法制备高性能氢气吸附用石墨烯

以液相氧化还原法为基础,并在分散剂十二烷基苯磺酸钠(SDBS)作用下制备得到高质量石墨烯,有效避免了在此过程中石墨烯大量团聚的现象.采用X射线衍射(XRD)、拉曼光谱(RS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和原子力显微镜(AFM)等分析手段对石墨烯样品进行了表征.XRD结果体现了石墨、氧化石墨和石墨烯晶型结构的区别;SEM和TEM结果显示石墨烯呈网格状,表面平整,缺陷少;AFM分析表明样品中单层石墨烯厚度约为1.3 nm,同时也存在少许双层结构.BET测试法得到石墨烯的比表面积高达1206 m2·g-1,考察了石墨烯在高压条件下对H2的吸附性能.通过对方法改进前后所制备的石墨烯样品进行比较,结果表明,十二烷基苯磺酸钠的加入有效地减小了石墨烯的大量团聚,且得到了高质量的石墨烯.在25和55℃条件下,高质量石墨烯对氢气的吸附量分别达到1.7％(w)和1.1％(w),比之前研究结果有了很大提高.     

Photoluminescence and electrochemical investigation of curcumin-reduced graphene oxide sheets

This paper reports on a novel low-temperature method for preparing curcumin-reduced graphene oxide (Cur-rGO) from graphene oxide (GO) and investigates their cyclic voltammetry (CV) and photoluminescence (PL) properties. GO sheets were synthesized using modified Hummers’ method and then were chemically reduced using polyphenol curcumin into graphene sheets. Atomic force microscopy, transmission electron microscopy and x-ray photoelectron spectroscopy were used to confirm the formation of Cur-rGO and revealed their functionalization with polyphenol curcumin. The electrochemical and optical properties of the Cur-rGO sheets were investigated using CV and PL spectroscopy. According to the PL and CV characterization for the Cur-rGO sheets, charges and resonant energy were transferred from curcumin molecules to the GO sheets’ surfaces. This arises from the bonding of the fluorescence curcumin molecules to the Cur-rGO surfaces, through π–π stacking of their aromatic rings. It should be noted that curcumin molecules act as electron donors, suppressing the fluorescence of the GO sheets while improving their electrochemical activities.     

Template‐free Fabrication of Hierarchical Macro‐/mesoporous N‐doped TiO2/graphene Oxide Composites with Enhanced Visible‐light Photocatalytic Activity

Hierarchical macro‐/mesoporous N‐doped TiO₂/graphene oxide (N‐TiO₂/GO) composites were prepared without using templates by the simple dropwise addition mixed solution of tetrabutyl titanate and ethanol containg graphene oxide (GO) to the ammonia solution, and then calcined at 350 °C. The as‐prepared samples were characterized by scanning electron microscopy (SEM), Brunauer‐Emmett‐Teller (BET) surface area, X‐ray diffraction (XRD), Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), and UV‐Vis absorption spectroscopy. The photocatalytic activity was evaluated by the photocatalytic degradation of methyl orange in an aqueous solution under visible‐light irradiation. The results show that N‐TiO₂/GO composites exhibited enhanced photocatalytic activity. GO content exhibited an obvious influence on photocatalytic performance, and the optimal GO addition content was 1 wt%. The enhanced photocatalytic activity could be attributed to the synergetic effects of three factors including the improved visible light absorption, the hierarchical macro‐mesoporous structure, and the efficient charge separation by GO.     

Hydrogel‐Assisted Transfer of Graphene Oxides into Nonpolar Organic Media for Oil Decontamination

In this work, graphene oxide (GO)‐loaded agarose hydrogel was transferred into oil such as hexadecane via stepwise solvent exchange with no chemical modification of the GO hydrophilic surface and the agarose network. After transfer, the GOs, loaded in the agarose network, could effectively and efficiently adsorb lipophilic dyes in oil via hydrogen bonding between the polar groups of the GOs and the dyes. The maximum adsorption capacity was 355.9 mg g^?1 for Nile red for instance, which is substantially larger than that of pristine agarose hydrogel and hydrophilic GO powder. The dye concentration for effective adsorption can be as low as 0.5 ppm. Thus, the present work demonstrates the promising potential of using hydrophilic adsorbents for efficient removal of polar impurities from oil.     

Dioxomolybdenum(VI) complex covalently attached to amino‐modified graphene oxide: heterogeneous catalyst for the epoxidation of alkenes

Transition metal salen complex MoO₂–salen was successfully tethered onto amino‐functionalized graphene oxide (designated as MoO₂–salen–GO), which was tested in the epoxidation of various alkenes using tert‐butylhydroperoxide or H₂O₂ as oxidant. Characterization results showed that dioxomolybdenum(VI) complex was successfully grafted onto the amino‐functionalized graphene oxide and the structure of the graphene oxide was well preserved after several stepwise synthesis procedures. Catalytic tests showed that heterogeneous catalyst MoO₂–salen–GO was more active than its homogeneous analogue MoO₂–salen in the epoxidation of cyclooctene due to site isolation. In addition, the MoO₂–salen–GO catalyst could be reused three times without significant loss of activity. Copyright © 2014 John Wiley & Sons, Ltd.